Resinous products derived from condensation products of cycloaliphatic ketones with guanidines, dicyandiamide, or biguanides



-' Patented Aug. 8, 1950 DENSATION PHATIC KETONES PRODUCTS OF CYCLOALI- WITH GUANIDINES,

DICYANDIAMIDE, OR BIGUANIDIS AndrenJ. Appelquest, Old Greenwich, Coma, al-

signor to American Cyanamid Comma-New York, N. Y a corporation oi Maine No Application October 16, 1046, Serial No. 703,468

3 Claims. (01. 26064) V This invention relates to resinous aldehyde condensation products and more particularly, to al.- dehyde condensation products of the reaction products of amidines with reactive ketones;

It is an object of the present invention to prepare improved resins.

Another object of the present invention is to prepare water-insoluble resins suitable for use in '-surface coatings and molding compositions.

v The above and other objects are attained by reacting an amidine such as biguanide, guanidine or dicyandiamide with a cycloaliphatic ketone such as cyclohexanone, followed by condensation of the resulting. reaction product with an aidehyde such as formaldehyde.

The invention will be described in greater detail in conjunction with the following specific examples in which proportions are given in parts by weight. The examples are merely illustrative 'and it is not intended that the scope of the invention should be limited to the details therein set forth.

EXAMPLE 1 164 parts of the condensation product of dicyandiamide and cyclohexanone (1.0 mol) 162 parts of slightly acidic 37% Formalin (2.0

mols as formaldehyde) The dicyandiamide condensation product and the Formalin are heated with stirring in asuitable vessel to about 140 C. during which heating water boils off and a hydrophobic resin forms. The resin is soluble in hydrochloric acid and when heated to 120-140 0., it first melts and then cures.

-- EXAMPLE 2 Lacquers are prepared by heating a mixture of the condensation product of dicyandiamide and cyclohexanone, Formalin, and butanol to boiling,

and distilling off water and butanol while adding dry butanol. Lacquers are prepared with a molar ratio of 3:1, formaldehyde to condensation prodnet, and with a 4:1 ratio.

EXAMPLE 3 181 parts of the condensation product of biguanide and cyclohexanone 1.0 mol) 162 parts of 37% Formalin (2.0 mols as formaldehyde) An exothermic reaction sets in immediately upon mixing of these two compounds. A tough mass which turns brittle on cooling is formed.

I The resin is white, insoluble in acid, alkali and water, and cured by the heat of reaction.-

. EXAMPLE 4 244 parts of the condensation product of biguanide acetate-and cyclohexanone (1.0 mol) 182 parts of 37% Formalin (2.0 mols as formaldehyde) 162 parts of 37% Form The ingredients are heated together with stirring to about C. during. which heating water boils on. A clear. yellow resin is obtained which is soluble in acid, alkali and water.

EXAMPLE 5 576 parts of the condensation product of cycloheiianone and phenyl biguanide carbonate (1.0 mo

162 parts of'3'l% Formalin (2.0 mole as formaldehyde) The two substances are mixed together and a hydrophobic resin forms after a short time. The resin will not cure.

EXAMPLE6 219 parts or the condensation product 0! dine and cyclohexanone 1.0 mol) hyde) The two substances are-mixed together and heated, with stirring, to about 140 C. During the heating period, water boils oif and a resin which is insoluble in acid, alkali and water is obtained.

Preparation of the condensation product 0! dieyandiamide and cyclohexanone 336 parts of dicyandiamide (4.0 mols) 600 parts of cyclohexanone (6.0 mols) The reactants are heated for 3 hours at I C. in the course of which time 61 parts (3.4 mols) of water are 'formed. The reaction product is washed with acetone and recrystallized from methanol. The product has a melting point of 230 C. and the following analysis:

Per cent Per cent Per cent 0 N Calculated for 0.31m. 2;. 3 1 a4. 15 i .1 35. 5a 57.83 7.33 35. 71

Since only one mole of ketone reacts per mole of dicyandiamide, the product is probably a substituted quinazoline with the reaction proceeding as follows:

' C CH:

2,4-diamino-5,6,7,8- tetrahydro-quinazoline guani- (2.0 mols as :ormame- I do not wish, however, to be limited to the above reaction mechanism since it is only theoretical.

Preparation the condensation product 0! btauanide and cyclohezanone 36 parts of biguanide (0.36 mol) 150 parts of cyclohexanone (1.5 mols) The materials are heated for hour at 140 C. during which time 8 parts (0.4 mol) of water are formed. An exothermic reaction proceeds rapidly and the product, which is soluble in water ind ethanol, solidifies. A\56% yield of a product melting at 238 C. and \having the following analysis is obtained:

Per cent Per cent Per me C H N Calculated I01 ClHuNs .f- 52. 71 g; Fmmd- 52: 62 7: 56 40100 Only one mole of ketonereacts per mole of biguanide and it appears that the reaction may be represented as follows:

4,6-diamino-2,2-pent& methylene-1,2-dihydro- 1,3.5-triazino This is merely a theory of reaction mechanism, however, and I do not wish to be limited thereto.

4 i 16 parts (0.9) 0! water are formed. No solid separates from the reaction mixture. The liquid product is diluted with acetone, 26 parts of water are added, and carbon dioxide is bubbled into the liquid to produce the carbonate. An 89% yield as carbonate 0! a material have the following analysis is obtained:

Per cent Per cent Per cent Calculated for cnnmNmoin; gags; ga Fmmd 58:63 0199 24:01

Preparation of the condensation product of guanidine and cuclohezanone 30 parts of guanidine (0.5 mol) 150 parts of cyclohexanone (1.5 mols) Percent Per cent Per cent C H N Calculated for CnHnNs.

Found www see

Since the guanidine-cyclohexanone reaction product and one prepared from g'uanidine and cyclohexylidene cyclohexanone are apparently identical, judging from the fact that a mixed melting point of the two shows no depression, the reaction apparently proceeds as follows:

Preparation of the condensation product of biguanide acetate and cyclohexanone 430 parts of biguanide acetate (2.! mols) 500 parts of cyclohexanone (5.0 mols) ,0! the condensation product of cyclohexanone and free biguanide is obtained after the solid reaction product has been filtered and washed with benzene.

Preparation of the condensation product of phenyl biguanide carbonate and cyclohemnone 177 parts of phenyl biguanide (1.0 mol) 150 parts of cyclohexanone (1.5 mols) The biguanide and the cyclohexanone are heated for A hour at 140 C. during which time 2-amino-4,4-pentamethylene-5,B-tetrmethylene-4,5-dihydropyrimidine I do not wish to be limited to this or any other particular theory of reaction mechanism, however.

Other amidines than those of the specific examples may be reacted with cycloaliphatic ketones to form resin intermediates useful in the process of the present invention. Among these are monoand .di-substituted biguanides and monoand di-substituted guanidines for example, N,N-dipheny1 biguanide, N,N-diphenyl biguanide, octadecyl biguanide, N,N- and N',N'- dioctadecyl biguanides, monobenzyl biguanide, N,N-dibenzyland N,N'-dibenzyl biguanides, N- ethyl-N'-benzyl biguanide, monofurfuryl biguanide, N,N'-difurfuryland N,N-difurfuryl biguanides, monoethyl biguanide, N,N-diethyl, and N,N'-diethyl biguanides, butyl biguanide, isobutyl biguanide, tert. butyl biguanide and the corresponding N,N= and N ,N-dibutyl biguanides, octyl biguanide, N,N- and N,N' dioc'tyl biguanidesetcq methyl guanidine, N,N- and N,N'-dimethyl guanidines, ethyl guanidine, N,N- and N,N' diethyl guanidine, N '-methyl-N-ethyl guanidine, phenyl guanidine, N,N-diphenyl guanidlne, N,N'-di-- phenyl guanidine, benzyl guanidine, N,N'- and N,N dibenzyl guanidines, furfuryl guanidine, N,N- and N,N-difurfuryl guanidines, butyl guanidine, isobutyl guanidine, tertiary butyl guanidine and the corresponding N,N"- and N,N-dibutyl guanidines, pctyl guanidine, N,N-dioctyland N,N'-dioctyl guanidines, octadecyl guanidine, N,N-dioctadecyl and N,N'-dioctadecyl guanidines, etc. The corresponding salts such as, the carbonates, acetates, etc., of the guanidines and biguanldes, for example, guanidine carbonate,

blguanide acetate; phenyl guanidine acetate, benn i i-onion and other similar cycloaliphatic ketones, may be used to advantage.

Resin intermediates prepared by condensing amidines of the type listed above and specified in the examples with cycloaliphatic ketones such as, for example, the condensation product of butyl guanidine'and cyclqhexanone, N,N-diethyl guanidine and cyclohexanoneguanidine and cyclopetanone, biguanide and cyclopentanone, etc.,

' may be resinifled with aldehydes other than formaldehyde, polymers of formaldehyde or other formaldehyde-yielding substances. A few sultabie aldehydes are benzaldehyde, acetaldehyde, crotonalclehyde, furfural, etc. These resin intermediates which are so resinifled are monomeric condensation products of amidine and ketone, preferably in a molar ratio of 1:1 to 1:2. They are relatively simple organic compounds and not complex polymers.

The new resins of the present invention may be mixed with fillers, pigments, etc., to obtain molding compositions which can be shaped under heat and pressure. Various fillers including wood flour, wood filler, paper dust, clay, zein, glass, wool. mica, granite dust, silk flock, cotton flock, steel wool, silicon carbide, paper, cloth, sand, etc., may be used. Suitable pigments are carbon black, iron blue, chrome yellow, lithopone, etc. On the other hand, no filler or pigment need be incorporated if not desired.

My new resins are also useful in coating compositions. Any suitable plasticizers or solvent softeners may be incorporated into mixtures or blends of the resins of the present invention, and high-boiling solvent softeners are particularly useful in the production of lacquers and printing inks. Thus, for example, compounds of the ester type such as diethyl or dibutyl phthalate, dibutyl sebacate, ethyl or butyl lactate, etc., solvents of the ketone type such as ethyl or butyl benzoyl benzoate, etc., chlorhydrins such as epichlorhydrin, etc., and such substances as phthalide, sulfonamides, glycol ethers, etc., may be admixed with my resins. In addition are high-boiling alcohols such ascetyl alcohol, lauryl alcohol, noctyl alcohol, capryl alcohol, cyclohexanol, methyl cyclohexanol, hydrofurfuryl alcohol, butanol, pentanol, mixtures of isomeric pentanols, etc. Solvents or softeners of other types may also be used, for example, solvent mineral oils, pine oil,

toluol, xylol, castor oil, other non-drying or semidrying oils and in general any of the solvents,

tries.

plasticizers or thinners now employed in the paint, lacquer, varnish and printing ink indus- Obviously, natural resins or other synthetic resins may be admixed with the resins 0f the present invention in order to obtain products suitable for particular purposes. Examples of a few of these are shellac, cellulose esters and others, urea resins, melamine resins, phenolic resins, alkyd resins, copolymers of unsaturated alkyd resins and unsaturated monomeric compounds, ester gum, etc. The resins may also be mixed with rubber or synthetic rubber if desired.

solvent of a formaldehyde condensation product according to claim 2.

Rm J. APPELQUEST.

REFERENCES CITED The following references are of record in the file of this patent:

H i STATES PATENTS Number Name Date 1,906,942 ter Horst May 2, 1933 1,952,060 Ellis Mar. 27, 1934 1,986,067 Paquln Jan. 1, 1935 2,323,898 D'Alelio July 13, 1943 2,325,376 DAlelio July 27, 1M3

Certificate of Correction Patent No. 2,517,824 August 8, 1950 ANDREN J. APPELQUEST It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Columns 3 and 4, right hand portion of last formula, for

-cn, --OH:

on, read om Q -o column 5, line 46, for the syllable petanone read pentanone;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 7th day of November, A. D. 1950.

l THOMAS F. MURPHY, 1 Assistant Gommz'ssz'aner of Patents. 

2. A FORMALDEHYDE CONDENSATION PRODUCT OF THE ORGANIC HEAT CONDENSATION PRODUCT OF DICYANDIAMIDE WITH A CYCLOALIPHATIC KETONE SELECTED FROM THE GROUP CONSISTING OF CYCLOHEXANONE, CYCLOHEXYLIDENE CYCLOHEXANONE, AND CYCLOPENTANONE IN A MOLAR RATION OF 1:1 TO 1:2, DICYANDIAMIDE TO KETONE. 